N, n-dialkenyl-alpha, alpha-diphenyl acetamides as herbicides



No Drawing. Filed Jan. 10, 1961, Ser. No. 81,702 11 Claims. (Cl. 712.6)

This invention pertains to novel chemical compounds, compositions, and a process. More particularly, the invention relates to novel N,N-dialkenyl-a,a-diphenylacetamides, herbicidal compositions containing the same, and a process for preventing germination of undesired plant seeds and controlling the growth of such plants.

The problem of weed damage to field crops is well known. Weeds damage field crops and reduce productivity by competing with the crop plants for mineral nutrients, nitrogen, water, and sunlight. In addition to economic damage to field crops, weeds such as dandelions and crabgrass frustrate the establishment and maintenance of uniform turfs on home lawns, golf courses, cemeteries, and public commons. Among the methods for combatting weeds that have been tried, selective chemical inhibition appears to hold promise of being efficacious and economical, and a great many chemical herbicides have been contrived.

An object of this invention is to provide compositions for preventing the germination of undesired plant seeds. A further object of the invention is to provide a means for preventing the germination of undesired plant seeds and for controlling the growth of noxious weeds in field crops and turf. A still further object of the invention is to provide a means for controlling noxious weeds such as Johnson grass, crabgrass, pigweed, quackgrass, wild oats, foxtail grasses, mustard (yellow rocket), purslane, lambsquarter, sheep sorrel, and the like in crops such as cereal grains, cotton, peanuts, beans, and strawberries, and in turf.

It has now been found in accordance with the invention that the novel N,N-dialkenyl-u, x-diphenylacetamides represented by the formula o lknl Q alkenyl wherein alkenyl is of from 3 to 4 carbon atoms, i.e., allyl, methallyl, 3-b-utenyl, and crotyl are effective preemergence herbicides and can be used in preventing germination of seeds and controlling the growth of plants by contacting said seeds and plants with a herbicidally effective amount thereof.

The novel N,N-dialkenyl-a,a-diphenylacetamides of this invention are readily prepared by substitution reaction between a diphenylacetyl halide, e.g., diphenylacetyl chloride, and the desired dialkenylamine [e.g., diallylamine, dimethallylamine (Tamele et al., Ind. Eng. Chem. 33, 115-120, 1941), N-rnethallylcrotylamine, ibid., di-3-butenylarnine (Reppe et al., Ann 596, 80-158, 1955), and dicrotylamine (Berthold, Chem. Ber. 90, 2743- 2747, 1957)] in the presence of an inert organic solvent. Suitable inert organic solvents include benzene, diethyl ether, dioxane, and toluene. .Stoichiometrically, the reaction requires one mole of amine for each mole of acid halide. However, the substitution releases one mole of hydrogen chloride; so an excess of amine, preferably at least one mole excess, should be provided. In lieu of an excess of the amine, another suitable acid acceptor, for example, triethylamine, pyridine, picoline, sodium hydroxide, and the like can be utilized The reaction can atent N,Ndialkenyl-a,wdiphenylacetamide be carried out at temperatures in the range of about 0 C. to about 100 C. or up to the reflux temperature of the solvent. The N,N-dialkenyl-u,a-diphenylacetamide product is recovered by conventional methods, for example, filtering, washing to remove amine salts, and recrystallization.

T-he herbicidal compositions according to the invention include solutions, emulsions, suspensions, dispersible powders, emulsifiable concentrates, granular formulations, and dusts. All of these compositions comprise the in dispersed or readily dispersible form and a carrier, with or without adjuvants. In general, selective inhibition of undesired weed species in the presence of field crops or in turf is obtained by employing a phytonomic carrier, that is to say, a carrier which can be applied to plants without phytotoxicity or other adverse effects. On the o h r hand, when general herbicidal activity is desired a phytotoxic carrier, for example, high-boiling mineral oil fractions or chlorohydro'canbons can be used.

The efficacy of N,N-dialkenyl-a,u-diphenylacetamides as pre-emergence herbicides is of high order, and the compounds can be applied at relatively low rates per acre for preventing the germination of seeds and controlling the growth of plants. For example, N,N- diallyl-a,a-diphenylacetamide gave complete or substantially complete suppression of crabgrass, foxtail grasses, Johnson grass, pigweed, and quickgrass when applied at the rate of 2.5 to 5 lbs. per acre to newly seeded plots. Little or no phytotoxic effect is apparent among field crop plants such as corn, wheat, rye, soybeans, and peanuts at these and even somewhat higher rates f application. At high rates of application, e.-g., at 15 to 30 lbs. per acre the compounds are phytotoxic to corn, wheat and rye; but legumes, such as peanuts, are not killed. Illustratively, excellent control of crabgrass in lawns has been obtained using concentrations of N,N- diallyl-a,a-diphenylacetamide ranging from 700 ppm. (parts per million) to 12,000 ppm. applied at the rate of 0.25 to 4 lbs. per acre without damage to the turf. In general, a desired rate of application can be achieved by distributing, over the area to be treated, an aqueous composition in accordance with the invention, containing from about 700 {LP-m. to about 30,000 ppm. of active ingredient. It will be understood, of course, that a choice of concentration of active ingredient depends upon the method of application as well as the type of composition and the degree of herbicidal control desired. In general, concentration is not critical within the. range indicated since an effective quantity of active ingredient can be applied to a given area by applying greater quantities of a low concentration than of a higher concentration. The concentration of active ingredient in the dispersib-le powder and emulsifiable concentrates from which the aqueous compositions are prepared can be as high as 99.5% by weight. The concentration of active ingredient in the dust and granular formulations of the invention can vary from about 0.25% to about 80% or more, but advantageously is of the order of 0.50% to 20%.

The granular formulations of this invention are prepared with about 0.25% to about 80%, preferably 0.50% to 20% by weight, of active ingredient and a granular carrier, for example, vermiculite, pyrophyllite, and attapulgite. The active ingredient can be dissolved in a volatile solvent such as methylene dichloride, acetone, and the like, and sprayed on the granular carrier as it is mixed and tumbled. The granules are then dried. The granular carrier can range in particle size from about 10 to about 60 mesh, preferably about 30 to 60 mesh.

about 80% by weight, preferably 0.50% to of the active ingredient with a solid pulverulent carrier which maintains the composition in a dry, free-flowing state. Since the N,N-dialkenyl-a,a-diphenylacetamidcs are solids at ordinary temperatures, the herbicidal dusts of the invention can be prepared by admixing with a solid diluent and then milling. Preferably, however, the active ingredient is dissolved in a volatile organic solvent, of the kinds indicated above, and then sprayed on the solid carrier so as to assure thorough distribution. The mixture is then dried and milled to the desired size, e.g., less than about 60 microns.

Solid carriers that can be used in the dust compositions of the invention include the natural clays such as China clay and bentonite, minerals in the natural state such .as talc, pyrophylli-te, quartz, diatomaceous earth, fullers earth, chalk, and rock phosphate, and the chemically modified minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, precipitated calcium silicate, and colloidal silica. The solid diluents which can be employed in the compositions also include-solid, compounded fertilizers. Such solid compositions can be applied to vegetation in the form of dusts by the use of conventional machinery.

A preferred composition, in accordance with the invention, is a dispersible powder which is prepared by incorporating a surfactant in a dust composition prepared as described above. Such a dispersible powder can be dispersed in water to any desired concentration and applied to vegetation by conventional spray equipment. Conveniently, the dispersible powders are formulated with higher concentrations of active ingredient than the dust compositions, for example, up to about 80%, preferably about 10% to 60%. Surfactants useful in preparing such dispersible powder compositions include alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene-sorbitan monolaurate, alkyl aryl polyether sulfates, alkyl aryl polyether alcohols, alkyl naphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty acids, and esters,

. sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, lignin sulfonates, and the like. A preferred class of surfactants includes blends of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77), blends of polyoxyethylene ethers and oil-soluble sulfonates (Emcol H-400), blends of alkyl aryl 'sulfonates and alkylphenoxy polyethoxy et hanols (Tritons X151, X-l61, and X-l71), e.g., about equal parts of sodium kerylbenzene sulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl aryl sulfonates and polyethoxylated vegetable oils (Agrimul N 8). It will be understood, of course, that the sulfate and sulfonate surfactants suggested above will preferably beused in the form of their soluble salts, for example, their sodium salts. All of these surfactants are capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1% or less. The dispersible powder compositions can be formulated with a mixture of surfactants of the types indicated if desired.

A suitable dispersible powder formulation is obtained by blending and milling 327 lbs. of Georgia clay, 4.5 lbs. of isooctylphenoxy polyethoxy ethanol (Triton X-100) as a wetting agent, 9 lbs. of a polymerized sodium salt of substituted benzoid long-chain sulfonic acid (Daxad 27) as a dispersing agent, and 113 lbs. of the active ingredient. The resulting formulation has the following percentage composition (parts herein are by weight unless otherwise specified).

. Percent Activeingredient Isooctylphenoxy polyethoxy ethanol 1 7 Percent Polymerized sodium salt of substituted benzoid longchain sulfonic acid 2 Georgia clay 72 This formulation, when dispersed in water at the rate of 10 lbs. per 100 gals, gives a spray formulation containing about 0.3% (3000 ppm.) active ingredient which can be applied to soil, plant growth media, or turf at the rate of 40 gals. per acre to give a total application of active ingredient of 1 lb. per acre.

The compounds of this invention can be applied to soil, plant growth media, and turf in aqueous sprays without a solid carrier. However, since the compounds them selves are relatively insoluble in water they are preferably dissolved in a suitable inert organic solvent carrier. Advantageously, the solvent carrier is immiscible with water so that an emulsion of the solvent carrier in water can be prepared. If, for example, a water-miscible solvent carrier such as ethanol is used the solvent carrier will dissolve in the water and any excess N,N-dialkenyl-a,adiphenylacetamide will be thrown out of solution. (The compounds dissolve in water to about 50 p.p.m.). In an emulsion, the solvent phase is dispersed in the water r phase and the active ingredient is held in solution in the I dialkenyl-u,a-diphenylacetamide that will hold the compound in solution over the range of concentrations useful for preventing germination of undesired seeds and controlling growth of plants.

The emulsifiable concentrates of the invention are prepared by dissolving the active ingredient and a surfactant in a substantially water-immiscible solvent carrier (i.e., a solvent carrier which is soluble in water to the extent of less than 2.5% by volume at temperatures of the order of 20 to 30 C.), for example, cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and high-boiling petroleum hydrocarbons such as kerosene, diesel oil, and the like. If desired, a cosolvent such as methyl ethyl ketone, acetone, isopropanol, and the like can be included with the solvent carrier in order to enhance the solubility of the active ingredient. Aqueous emulsions are then prepared by mixing with Water to give any desired concentration of active ingredient. The surfactants which can be employed in the aqueous emulsions of the invention are those types noted above. Mixtures of surfactants can be employed if desired.

Advantageously, the concentration of active ingredient in the emulsifiable concentrates can range from about 5% to about 50% by weight, preferably from about 10% to 40%. A concentrate comprising 20% (by weight) ,of the compound dissolved in a water-immiscible solvent of the kind noted above can be admixed with an aqueous medium in the proportions of 13 ml. of concentrate with 1 gal. of medium to give a mixture containing 700 parts of active ingredient per million parts of liquid carrier. Similarly, 1 qt. of a 20% concentrate mixed with 40 gals. of water provides about 1200 ppm. of active ingredient. In the same manner, more concentrated solutions of active ingredient can be prepared.

The concentrate compositions of the invention which are intended for use in the form of aqueous dispersions or emulsions can also comprise a humectant, that is to say, an agent which will delay the drying of the composition in contact with material to which it has been applied. Suitable humectants include glycerol, diethylene glycol, solubilized lignins, such as calcium lignosulfonate, and the like.

The rates of application to soils, plant growth media, or turf to be protected from noxious weeds will depend upon the species of vegetation to be controlled, the presence or absence of desirable species, the season of year at which treatment is undertaken, and the method and efficiency of application. In general, selective herbicidal activity is obtained when the compounds are applied at the rate of about 0.125 to about 15 lbs. per acre, preferably at the rate of 0.25 to 5 lbs. per acre.

The compositions containing N,N-dialkenyl-a,a-diphenylacetamides, according to the invention, can be applied to soil, plant growth media, and turf by conventional methods. For example, an area of soil can be treated prior to or after seeding by spraying wettable powder suspensions, emulsions, or solutions from boomtype power sprayers or from hand-operated knapsack Sprayers. Dusts can be applied by power dusters, or by hand-operated dusters. Dusts and granular formulations can also be applied at the time of seeding in bands spanning the seeded rows.

The following examples are illustrative of the process and products of the present invention, but are not to be construed as limiting.

Example 1.Preparation of N,N-Diallyl-u,u-Diphenylacetamide To a solution of 23 g (0.1 mole) of diphenylacetyl chloride in 500 ml. of diethyl ether was added 24.29 g.

(0.25 mole )of diallylamine. A precipitate began to form, and the reaction mixture was stirred for 30 minutes at about 25 C. The precipitate was collected on a filter and the filter cake was washed with 200 ml. of (w./v.) potassium hydroxide soluttion, and then with 200 mlsof water. The washed cake was recrystallized from Skellysolve B (essentially a mixture of methyl-substituted pentanes and n-hexane having a boiling range of 140 to 160 Fahrenheit) to give 16.85 g. of N,N-diallyl-a,o-diphenylacetamide having a melting point of 49 to 50 C.

Analysis.-Calculated for C H NO: C, 82.44; H, 7.26; N, 4.81. Found: C, 82.46; H, 7.47; N, 4.84.

Following the same procedure but substituting dimethallylamine, dicrotylamine, N-inethallylcrotylamine, and di- 3-butenylamine for diallylamine there were obtained N,N-dimethallyl-m,a-diphenylacetamide, N,N-dicrotyl-a,adiphenylacetamide, N-methallyl N crotyl-a,a-diphenylacetamide, and N,N-di(3-butenyl)-a,ot-diphenylacetamide, respectively.

Example 2 A fine granular formulation having the following percentage composition:

Percent N,N-diallyl-u,a-diphenylacetamide 3.7

Vermiculite (30/60 mesh) 96.3 was prepared by spraying a solution of 220 g. of N,N diallyl-a,a-diphenylacetamide in 1000 ml. of methylene chloride on 5780 g. of vermiculite (30 to 60 mesh) while the vermiculite was being tumbled and stirred so as to assure even distribution. The methylene chloride was then evaporated, leaving the N,N-diallyl-rx,a-diphenylacetamide adsorbed on the vermiculite, and the vermiculite was pulverized.

The herbicidal efiicacy of the formulation was then determined by spreading the treated vermiculite on test plots of soil planted to rows of crabgrass, green foxtail, yellow foxtail, Johnson grass, wheat, corn, rye, and peanuts. After 21 days the inhibition of seed germination and plant vgrowth were noted, when compared with control plots of the same area and cultural treatment. The results are shown in Table I...

' diphenylacetamide, -N-methallyl N crotyl-a z-diphenyh' In the same manner granular compositions containing N,N-dimethallyl-a,a-diphenylacetamide, N,N-dicrotyl-a,m-

acetamide, and N,N-di(3-buteny1)-a,a-diphenylacetamide were prepared and tested with similar results.

Example 3 A dispersible powder concentrate having the following percentage composition:

Percent N,N-diallyl-a,a-diphenylacetamide 45.8 Polymerized sodium salt of substituted benzoid longchain sulfonic acid (Daxad 27) 9.2 Kaolinite 45.0

was preparedby mixing 250 g. of N,N-diallyl-a,a-diphenylacetamide, 50 g. of a polymerized sodium salt of substituted benzoid long-chain sulfonic acid (Daxad 27 and 245 g. of kaolinite. The mixture was milled to a particles size averaging 5 to 30 microns.' It was suspended in 10 gals. of water, giving an aqueous spray containing about 6000 parts per million of active ingredient.

Example 4 An e'mulsifiable concentrate having the following percentage composition:

Percent. N,N-diallyl-a,u-diphenylacetamide 15.0 Technical alkyl naphthalene boiling at 238 to 293 C. (Velsicol ARSO) 19.7 Xylene 17.4 Isopropanol 17.4 Ethylene dichloride 25.4

Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) was prepared by mixing,15.0 lbs. of N,N-diallyl-u,a-diphenylacetamide, 19.7 lbs. of Velsicol AR 50, 17.4 lbs. of xylene, 17.4 lbs. of isopropanol, 25.4 lbs. of ethylene dichloride, and 5.1 lbs. of Triton X-151.

6.67 lbs. of the concentrate mixed with 10 gals. of water gave a spray emulsion containing 12,000 p.p.m. of N,N- diallyl-a,a-diphenylacetamide.

Example 5 Anemulsifiable concentrate having the following percentage composition:

Percent N,N-diallyl-a,a-diphenylacetamide 40.0 Technical alkyl naphthalene boiling at 238 to 293C. (Velsicol ARSO) 13.7 Xylene 12.3 Isopropanol 11.3 Ethylene dichloride 17.7 Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) -c 5.0

was prepared by mixing 40.0 lbs. of N,N-diallyl-a,adiphenylacetamide, 13.7 lbs. of Velsicol AR50, 12.3 lbs. of xylene, 11.3 lbs. of isopropanol, 17.7 lbs. of ethylene dichloride, and 5.0 lbs. of Triton X-151.

1.67 lbs. of the concentrate mixed with 10 gals. of water gave a spray emulsion containing 8,000 p.p.m. of N,N-diallyl-a,u-diphenylacetamide.

7 Example 6 A Wettable powder concentrate having the following percentage composition:

Percent N,Ndiallyl-u,a-ldiphenylacetamide 50 Kaolinite clay (finely divided) 46 Sodium salt of condensed mononaphthalene sulfonic acid (Lomar D) 4 A granular formulation having the following percentage composition Percent N,N-di llylre, -diphenyl c tamide 1 Pyrophyllite 30/ 60 mesh) 99 was prepared by dissolving 1.0 lb. of N,N-diallyl-a,u-diphenylacetamide. in 10.0 1. of ethylene dichloride and spraying the, solution on 99.0 lbs. of pyrophyllite. The granules were dried and, then packaged for use.

. -I claim:

1. Thecompound N,N- dialkenylu diphenylacetamide wherein alkenyl is of from 3 to 4 carbon atoms.

2 The compound N,N-dially-l- ,u-diphenylacetamide. 3. H erb icidal composition of matter comprising N,N- dialkenyl-a, c-diphenylacetamide wherein alkenyl is of from 3 to 4 carbon atoms, inclusive, as the essential active ingredient and a dispersible carrier therefor.

4. The composition according to claim 3 containing a surfactant.

5. The, composition according to claim 4 wherein thedispersible carrier is dispersible powder.

6. Emulsifiable concentrate comprising N,N-dialkenyle,u-diphenylacetarnide wherein alkenyl is of from 3 to.

4 carbon atoms, inclusive, a substantially water-immiscible solvent carrier therefor, and a surfactant, said N,N-dialkenyl-a,a-diphenylacetamide constituting 5% to 50% of the composition.

7. Herbicidal composition of matter comprising N,N- diallyl-a,a-diphenylacetamide as the essential active ingredient, and a solid particulate carrier therefor having an average particle size up to 10 mesh.

8. Herbicidal composition of matter comprising, N,N- dialkenyl-or,or-diphenylacetamidev wherein alkenyl is of from 3 to 4 carbon atoms, inclusive, as the essential active ingredient, and a solid particulate carrier therefor having an average particle size up to 10 mesh.

9. The method of preventing germination of seeds and controlling growth of plants which comprises contacting said seeds and plants with a herbicidally effective amount of N,N-dialkenyl-ma-diphenyhcetamide wherein alkenyl is of'from 3 to 4 carbon atoms, inclusive.

10. The method of preventing germination of seeds and controlling growth of plants which comprises contacting said seeds and plants With a herbicidally effective amount of N,N-diallyl-a,wdiphenylacetamide.

11'. Emulsifiable concentrate comprising N,N-di'allylu,a-diphenylacetamide, a substantially water-immiscible solvent carrier therefor, and a surfactant, said N,N-diallylu,a-diphenylacetamide constituting 5% to 50% of the composition.

No references cited. 

1. THE COMPOUND N,N-DIALKENYL- A,A -DIPHENYLACETAMIDE WHEREIN "ALKENYLC" IS OF FROM 3 TO 4 CARBON ATOMS.
 6. SEMULLSIFIABLE CONCENTRATE COMPRISISNG N,N-DIALKENYLA,A-DDIPHENYLACETAMMIDE WHEREIN "ALKENYL" IS OF FROM 3 TO SSOLVENT CARRIER THEREFOR, AND A SURFACTANT, SAIID N,N-DIALKENYL-A,A-DIPHENYLACETAMIDE CONSTITUTING 5% TO 50% OF THE COMPOSITION.
 9. THE METHOD OF PREVENTING GERMINATION OF SEEDS AND CONTROLLING GROWTH OF PLANTS WHICH COMPRISES CONTACTING SAID SEEDS AND PLANTS WITH A HERBICIDALLY EFFECTIVE AMOUNT OOF N,N-DIIALKKENYL-A,A-DIPHENYLACEETAMIDE WHEREIN "ALKENYL" IS OF FROM 3 TO 4 CARBON ATOMS, INCLUSIVE. 